Switchable Bioelectrocatalysis Controlled by Dual Stimuli-Responsive Polymeric Interface

The engineering of bionanointerfaces using stimuli-responsive polymers offers a new dimension in the design of novel bioelectronic interfaces. The integration of electrode surfaces with stimuli-responsive molecular cues provides a direct control and ability to switch and tune physical and chemical properties of bioelectronic interfaces in various biodevices. Here, we report a dual-responsive biointerface employing a positively responding dual-switchable polymer, poly­(NIPAAm-<i>co</i>-DEAEMA)-<i>b-</i>HEAAm, to control and regulate enzyme-based bioelectrocatalysis. The design interface exhibits reversible activation–deactivation of bioelectrocatalytic reactions in response to change in temperature and in pH, which allows manipulation of biomolecular interactions to produce on/off switchable conditions. Using electrochemical measurements, we demonstrate that interfacial bioelectrochemical properties can be tuned over a modest range of temperature (i.e., 20–60 °C) and pH (i.e., pH 4–8) of the medium. The resulting dual-switchable interface may have important implications not only for the design of responsive biocatalysis and on-demand operation of biosensors, but also as an aid to elucidating electron-transport pathways and mechanisms in living organisms by mimicking the dynamic properties of complex biological environments and processes

Studies on Bacterial Proteins Corona Interaction with Saponin Imprinted ZnO Nanohoneycombs and Their Toxic Responses

Molecular imprinting generates robust, efficient, and highly mesoporous surfaces for biointeractions. Mechanistic interfacial interaction between the surface of core substrate and protein corona is crucial to understand the substantial microbial toxic responses at a nanoscale. In this study, we have focused on the mechanistic interactions between synthesized saponin imprinted zinc oxide nanohoneycombs (SIZnO NHs), average size 80–125 nm, surface area 20.27 m²/g, average pore density 0.23 pore/nm and number-average pore size 3.74 nm and proteins corona of bacteria. The produced SIZnO NHs as potential antifungal and antibacterial agents have been studied on <i>Sclerotium rolfsii (S. rolfsii)</i>, <i>Pythium debarynum (P. debarynum) and Escherichia coli (E. coli)</i>, <i>Staphylococcus aureus (S. aureus)</i>, respectively. SIZnO NHs exhibited the highest antibacterial (∼50%) and antifungal (∼40%) activity against Gram-negative bacteria (<i>E. coli</i>) and fungus (<i>P. debarynum)</i>, respectively at concentration of 0.1 mol. Scanning electron spectroscopy (SEM) observation showed that the ZnO NHs ruptured the cell wall of bacteria and internalized into the cell. The molecular docking studies were carried out using binding proteins present in the gram negative bacteria (<i>lipopolysaccharide</i> and <i>lipocalin Blc</i>) and gram positive bacteria (Staphylococcal Protein A, SpA). It was envisaged that the proteins present in the bacterial cell wall were found to interact and adsorb on the surface of SIZnO NHs thereby blocking the active sites of the proteins used for cell wall synthesis. The binding affinity and interaction energies were higher in the case of binding proteins present in gram negative bacteria as compared to that of gram positive bacteria. In addition, a kinetic mathematical model (KMM) was developed in MATLAB to predict the internalization in the bacterial cellular uptake of the ZnO NHs for better understanding of their controlled toxicity. The results obtained from KMM exhibited a good agreement with the experimental data. Exploration of mechanistic interactions, as well as the formation of bioconjugate of proteins and ZnO NHs would play a key role to interpret more complex biological systems in nature